Treating hydrocarbon fluids



March 6, 1945. J. R. SCHONBERG TREATING `HYDROCARBON FLUIDS Filed Oct. 1, 1940 3 Sheets-Sheet l III mm, wm, T

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March 6, 1945. 1. R. scHoNBERG TREATING HYDROCARBON FLUIDS Ffiled Oct. l, 1940 3 Sheets-Sheet 2 A @Q @Q 65% III llll' Q NN MNHN

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Patented Mar. 6, 1945 TREATING HYDROCARBON FLUIDS l Jackson R. SchonbergLWestield, N. J., assgiior f to Standard Oil Development Company, a cor'- poraton of Delaware i Application october 1, v1940, sei-ning. 359.195'

s Claims. `(MC1. 19e-52) This invention relates to the catalytic conver sion of hydrocarbons. f

y When using powdered catalyst for the conversion of hydrocarbons, where the hydrocarbonvapors and powdered catalyst are passed through a reaction zone, it is necessary to remove substantially all of the powdered catalyst from the reaction'products in order to have an economical process. If substantiallyA allof the powdered catalyst is not removed, some of the finer powdered catalyst will leave the systemwith the gases and this loss will be a continuous one. Generally a separator such as a cyclone separator is used but the vapors leaving such a separator still contain an appreciable amount of powdered catalyst.

According tovmy invention the powdered catalyst is removed substantially lcompletely -from the reaction product vapors. `In the preferred form of my invention the reaction products in vapor form are passed `to a suitable separating device such as a cyclone separator or the ,like to separatevapors from most of the powdered catalyst. yThe vapors leaving the separating device contain an appreciable amount of powdered catalyst and according to my invention, these i vapors are then passed to a suitable chamber wherein they are mixed with a relatively heavy oil as a reilux liquid to wash out or scrub out re- 4- maining powdered catalyst in the vapors. At the same time there is a condensation of the heavy fractions in the vapors `and this condensation provides additional reliuxl liquid for scrubbing or washing the vapors. The remaining vapors are then passed to suitable fractionatingl'equipment to separate desired products. c

The scrubbing oil containing the catalyst pow.- der is withdrawn from the scrubbing chamber and filtered toremove the catalyst particles from the oil and the filtered catalyst is regenerated in any suitable manner, al1 or part of the ltered oil being recycled tothe scrubbing chamber as reflux. 'Fresh oil may be added to the scrubbing chamber as reflux or scrubbing liquid. Inrthe filtering step continuous filters are preferably used. w

The powdered catalyst separated from the ref action product vaporsin the separating device is steamed to separate oilA therefrom. During the steaming operation some of the catalyst powder is carried along with the steamandpreferably all or part of the steamed powdered catalyst mayr be mixed with the reux oil from the scrubbing chamber and the entire mixture filtered. The powdered catalyst `after regeneration is preferably recycled to the reaction zone with additional quantities of hydrocarbons to be converted.

A portion or portions ofthe catalyst separated from the reaction products in the separating device may be introduced into the-reaction zone at one point or spaced pointsto increase the concentration of the catalyst in the hydrocarbon ras the conversion progresses.- f f I In another form of the invention thevapors -from theseparating 4device and. all or a portionl of the separated powderedv catalyst'may be passed to one scrubbing chamber, or allof the powdered catalyst mayberemoved and regenerated. The

f reaction product vapors are scrubbed or washed this steam containing'some catalyst particles is y passed tothe scrubbing chamber so as to remove thecatalyst particles from the steam. 'Ihe powdered catalyst after steamingis regenerated,

in any suitable'manner as by-.burning; Ifdesired,

with reux oil tov scrub out` or vwash out remaining powdered catalyst from the vapors leaving the separating devicel and which arev introduced into the scrubbing chamber. In the above forms --of my invention, the reaction chamber or zone is provided with a spiral baille to give the mixture 'of hydrocarbon vapors and powdered'catalyst a spiral path through the reaction zone. In a third form of my invention, the reaction ychamber is placed horizontally and the hydro- Y rcarbon vapors and powdered catalyst are introduced into one end, of vthe reaction chamber. The reaction products and some powdered catalyst are removed from a point adjacent the other end of the horizontally arranged reaction chamber. In this form of my invention I :take advantage ofthe natural tendency of the catalyst particles to separate by gravity. As the vapors and powdered catalyst pass horizontally through the reaction chamber, the catalyst par-ticlestend to `settle out and collect on'they bottom fof the reaction chamber. These-catalyst. particles are removed and regenerated in anysuitable manner. The reaction products in vapor form-and some of the finer particlescf catalyst leave the other end of the reaction chamberand are passed through a separating devicesuchas a cyclone separator to separate vapors from vpowdered' catalyst.-A The vapors leaving the separating device are introduced into a scrubbing chamber similar f to those described above. 1A portion or portions of the separated catalyst from the separating de- JlIn myinvention thecatalyst particles are l Vsubstantiallyy completely valporize the oil.

through which a relativelyheavy hydrocarbon.

oil such as gas oil or the like is passed by means of pump l2. used. The hydrocarbon oil' is passed through a heating coil I4 arranged in a furnace or heater lpto raise the temperature of the oil and to The heated hydrocarbon vapors leave` the heating coil- I4 and arepassed through lineV IB and into the*` linej ZU'Where they are mixedwith powdered catalystjintroduced.through nozzle or pipe 22. The pfowderedfcatalyst is fed tothe pipe 2- by meansfof the screw niechanisml'lfll- 4 The mixture of hydrocarbon` vapors and powdered catalyst is introduced into thelower portion ofthe reaction chamber Zwhichiis Shown as' a vertically arranged cylindrical chamber. The interior ofthe reaction chamber 2`8 is' providedwith avcontinuou'svspiralbalile'32 which is arranged around; a' vertical axis; 3'32 TheV spiral liaile'r" may be stationary' or rotatable' but is preferably stationary; The'spii'alba'fe is so Dircportionedasfto' vprovide the proper'velocity of the catalyst aindhydrocarbon vapor mixturethrough thereaction' chamber andv also to provide the propertimeof Contact tol eiect the desired ex'- tentor conversion.- By using a spiralbaiile, it is possible to reduce the length of` the reaction chamber anclin this' way small equipmentv may be used.'

'Ihe-reactionproducts and the powdered catalyst leave, theV top ofthe reaction chamber throughline 3Y4and are introduced' into a separatingV` device A36|` of" suitable construction. As shownin the' drawin'gs, the separating device is a cyclone separator but otherV separating devices ma-ybeu'sed.-A In the' separator 36, the reaction pro-ducts pr products of conversion are separated from a large' portion of thepowdered catalyst, the vapors passing overhead through' line 38'a'nd the' dry powderedA catalyst particles collecting in the' collecting chamber 42. The vapors passing through line ."1'8 are further' treatedv according to myinventionto separate substantially all ofthe catalyst particles therefrom and this will' be' described(k in. greater detail yhereinafter;A

The' catalystparticles'collectingin the lower portion' ofthe collecting chamber' 452V are withdrawn therefrom 'by vmeans of a" star feeder M andare passedthrough line 46; Allfo'r a portion ofthe'` separated catalyst particles mayy be rel turned-ltd the reaction chamber.` In the draw#- ingsI have shown branch valved'lines 48, 52 and 5`4for introducing' the separated catalyst par- Other hydrocarbon fluids may be ticles'finto the reaction chamber 28 at spaced points; ForA example. linell communicates with the' upper'portion' of" the reactionchamber` 28, line-52l communicates with an intermediate portion' of-'the reaction chamber 2 8` and line v'.511' communicates with thev lower portion of the reaction chamber 28. By returning the catalyst particles to the different places in the reaction chamber, the concentration of the catalyst in the hydrocarbon vapors is changed and in the particular form shown, the concentration'of the catalyst increases as the hydrocarbon vapors pass through the reaction chamber or as the conversion progresses. These branch lines may be placed at other points in the reaction chamber and I am not to be restricted to the exact location nor exact number shown in the drawings. If desired, jets of steam or vaporized hydrocarbons from line lo may be introduced into the respective branch lines 48, 52 and 54 through lines 55, 58 and 6,2` to facilita-te introduction of the catalyst particles into the reaction chamber.

During the conversion operation, the catalyst particles become covered with carbonaceous deposits which reduce the activity of the powdered catalyst. In order to maintain the activity, it is necessary to regenerate the catalyst particles which hadbeen used in the conversion operation. One form of regeneratio-n comprises mixing the catalyst particles with air orl other containing* free oxygen and burning the carbonaceous deposit from the' catalyst' particles. This regeneration step produces large quantities of heat and itr is necessary to carefully control the tempera`- ture during regeneration so as not to destroy the activity of the catalyst.

The powdered catalyst to beregenerated leaving the collecting chamberfd? through line46 is passed through line B4' andl introduced intothe upper portion of a steamingchamber 65: The chamber' GB is provided withinclined baflles' 68 andcones 'IZ` Steam isintroducedv through@ line it? into` the lower'portionof the' steaming chamber 6B and" passes upwardly ,through the cha-mber; The catalyst particles fall downwardly in the chamber'GE arid--r the baflles'andicon'es provide intimate contact between the-'steam andlthe'ca't'alyst particles and in this way the catalystparticles are de-oiled. During this steamingopera'- tion) some of the smaller particles of catalyst' are carried along with the outgoing steamand this outgoing steam leaves the top of the chamber 66 through line T6 and is introduced int'o the lower vportion' of a', second separating device T8 tosep'arate the catalyst particles from the' steam as-will be presently described in greater detail.

The steamed and de-oiled catalyst particles collect at. the bottom of the cham-ber GB'and' are withdrawn'A therefrom by means` of line 82.- The further treatment of these catalyst' particles will be describedin greater detail hereinafter.

Returning now to the' second separating chamber 18, it will be seen thatthe vaporous reaction products or products' of conversion-leaving the rst separating device 3G through line 33,` are introduce'dinto the lower'portion of the second separating? device 18. The second separatinglde vice' 'I8' is provided with a plurality of inclined bafes 54 and cones -86 forproviding'intimate contact between the reiiux'o'r 'scrubbing oil introduced" into the upper portion of the separating device 18 by means of line 88 and the gas or vapor steamsintroduced into the' lower'portion of the separating device l8; This'rei'lux oil is preferably a relatively heavy oil substantiallyV free of light constituents. ForV example, the condensate oil or bottoms from the fractionator (not shown), wherein the vapors from" the second separator i3 Yand passing throughline 92` are fractionated, may be used. y

As `above pointed out, the products of conversionpassingthroughline 38' andthe steam. passing through line I6 contain catalyst particles and the second separating device '18 is provided for substantially completely removing such catalyst particles from the vapors andv gases. The vapors and gases after being scrubbed or washed by the reflux liquid, pass overhead through line 92 and are further treated in any suitable manner as by fractionation, for example, to separate desired products.

During the scrubbing of the vapors and gases theheavier fractions in the vapors introduced through line 38 are condensed and these heavy fractionsare added to the reflux liquid and a part of the total liquid is preferably recycled as reflux liquid. Means are also provided by line 94 for introducing a fresh oil as reiiux liquid for introduction into the top portion of the second separating device 1S. The reflux liquid and the heavier fractions which were condensed in the separating device 18, together with the catalyst particles scrubbed out of the vapors and gases are withdrawn from the bottom of the second device 'I3 by means of line 9B, passed through cooler 98 to reduce the temperature of the liquid and the cooled liquid is then passed through filter |92 to separate the catalyst particles from the liquid oil. Preferably the lter |02 is a continuous lter. The oil which is separated during the ltering is passed through line |04.by pump Iilhand is further cooled by 30 means of cooler |58 and is then-returned as redux liquid to the top of tlfe second separating device 18. It is to be noted that while the reflux liquid is hot, it4 is ata lower temperature thanthe products of conversion passing through the 'sepan rating device 'I8 and in this way condensation of the heavier fractions in the reaction products is y brought about. In addition, the reaction product vapors are desuperheated. A portion of the filtered oil may bel withdrawn from the system through line IIB, if desired. Y

The filtered catalyst particles are taken from the filter and passed through line I|2 to a collecting chamber H4. It is preferable to further treat these ltered catalyst particles in any suitable manner before introducing them into the chamber or hopper ||4 so as to remove oil from the catalyst particles. In one method the catalyst particles may be washed relatively free of s oil by using a lght wash liquid such as naphtha rerun bottoms and this light liquid can then'V be removed by steaming. The resulting catalyst particles are substantially dry and can be conveyed pneumatically. or the filtered catalyst may be flushed from the lter and pumped as a slurry te the regeneration zone. The oil used for flushing'should be a cheap refinery fuel such as heavy pitch or cracked tar. y The steamed catalyst particles leaving the steaming chamber 55 through line 82 may be either mixed with the reflux liquid 'passing A through line S5 and filter Ill2 orpthe steamed catalyst particles Amay be directly passed to the regeneration zone. Or,y a part of the steamed catalyst particles may be passed to the regeneration Zone and the rest mixed with the oil slurry containing reflux liquid withdrawn from the bottom of the secondl separatingdevice 18. A line IIS is provided for mixingthe steamed catalyst particles with the oil slurry containing reflux liquid and a line I8 is provided for transferring the steamed catalyst particles to the hopper I I4.

The catalyst particles collecting in the hopper ||4 are withdrawn. from the bottom thereof by means of a screw mechanism-i 22 which is positioned in a barrel |24. The screw mechanism is rotated by any suitable" means as a. pulley I 26. The catalyst particles which are to be regenerated are introduced into a dispersing chamber |28 5 where they are mixed with air introduced through line |32. The suspension of catalyst particles in airis then passed through line |34 and heater |35` for raising the temperature of the catalyst particlesv to about 850 F. so that burning of the car- 10 bonaceous deposits on the catalystparticles will be initiated. The mixture of catalyst particles and air-is then passed through a heat exchange chamber |35 for removing heat from the catalyst suspension during regeneration. As the carbonaceous material burns, there is a large production of heat and it is necessary to remove this heat in order to prevent overheating of the catalyst particles. A salt bath or the like may be used to remove the heat by indirect heat exchange during regeneration. The regenerated catalyst and products of combustion leave the heat exchanger |36 through' line troduced into a separating chamber |42 of any suitable construction for separating products of combustion from regenerated catalyst particles.

A cyclone separator'r or separators may be used.'

The gaseous products leave the topof the separator |42 through line |45. .Steam is preferably introduced in the lower portion of the chamber |42 by means of linek |44 in order to remove any free oxygen which may be present in the chamber |42.

The regenerated catalyst particles collect-,fin the bottom of the chamber I 42 and are withdrawn -therefrom by means of star feeder |48 and are introduced into a hopper |52 from vwhichythey pass into a barrel |54.

The` screw mechanism 24, above described, is 40 positioned in the barrel |54. Suitable means such as pulley |56 are provided for rotating the screw mechanism.`r The regenerated catalyst particles are then introduced into a stream of hydrocarbon vapors for another conversion operation. Fresh catalyst may be introduced into hopper |52 by means of line |58.

The form of my invention shown in Figure 2 of the drawings will now be described. The apparatus shown in Figure 2 differs from that shown in Figure 1 mainly in that one separator is used for separating the catalyst particles from vapors by means of areflux liquid rather than two separators" as shown in Figure 1. Up to and includingv the ,first separating device 36, discharge line 46 and branch lines 48, 52, and 54, the apparatus is substantially the same and the same reference characters have been used as in Figure 1 to designate the same parts. The regeneration apparatus in Figure 2 is substantially the same 'as inFig- G0 use l and/the same reference characters have been used to designate the same parts.

In Figure 2 the separated catalyst particles from the chamber 42 are passed through the star feeder 4.4 and into line 4t. Some of the sepaa5 rated vcatalyst is returned to the reaction chamber at spaced points by branched lines 43, 52 and 54 similar to that shown in Figure l. All or a portion of the catalyst separated from the chamber 42 may be passed through line |66' into a separating device |58 provided with inclined baffles |22 and cones I'I4. The catalyst particles are introduced into the lower portion of the separating chamber Ill. The vapors passing overhead from thev-rst separating device 36 and containing re.- action products and some catalyst particles are |38 and the regenerated catalyst particles areinpassed' through line'V 38 andv introduced into an intermediate portion ofthe second separating device |68.

` Hot reflux liquid is introduced into the top portion of the separating chamber |68 by means of line |16 and spray head The reflux liquid flows countercurrent to the vapors containing catalyst particles and by means of the baiiles |72 and cones IM intimate contact is established between the liquid and the vapors to obtain scrubbing and washing action.

Steam is preferably introduced into the lower portion of the separating chamber U53 by means of line to remove oil from the catalyst particles. v

The catalyst withdrawn from the bottom ofthe chamber 42 through line 46 may be directly passed to the regeneration zone by means ofV line |19. Preferably the catalyst is steamed and de-oiled before being sent to the regeneration zone.

The roiiux liquid introduced into the second separating chamber |68 is at a lowertemperature than the reaction product vapors and b'ecause of this, some of the heavy fractions in the reaction product vapors are condensed. This assists in the removal of the small catalyst particles from the vapors and gases. The remaining vapors passoverhead through line |82 and are further treated as by fractionation to separate desired products. The reflux liquid and the heavy fractions together With the catalyst 'particles scrubbed out of the vapors and gases are withdrawn from the bottom of the separating chamber |68- by means of line |82, are cooled by means of cooler H36 and then filtered in a continuous filter or the like S8. The catalyst particles removed from the p ferent reaction chamber and a different arrangel ment of the apparatus. In this form of the inventicn. hydrocarbon vapors obtained in any suitable manner are passed through line 202 and mixed `with powdered catalyst passing through line 201i. end of an elongated horizontally arranged reaction chamber 206. The reaction chamber is provided with an inclined bottom 201. As the hydrocarbon vapors and catalyst pass substantially horizontally through the reaction chamber, there is a natural tendency for the catalyst particles to separate and they fall to the bottom ofthe reaction chamber where they are collected. The powdered catalyst after settling is removed through line 2|2 and may be regenerated in any 'suitable manner before being recycled for use in another conversion operation. The vaporous products of conversion containing some catalyst particles leave the other end of the 'reaction chamber and are passed through line 2M into a first separating device 216 for separating vapors and gases from solid catalyst particles. This separation is not completeA and some catalyst particles go overhead with the reaction product vapors through line 2|8. The solid cata- Fresh oil may be added as reflux liquid .l

The mixture is introduced into one .Y

lyst particles separated in the separator2|6 are withdrawn from the bottom thereof and passed through line 222. Portions of this catalyst may be returned and introduced into the reaction.

chamber 206 by means of branch lines 224, 226 and 228. By introducing the catalyst at spaced points, the catalyst concentration may be varied asthe' conversion progresses through the reaction chamber 206.

Another portion of the catalyst particles passing through line 222 or all of the catalyst particles may be passed through line 232 to a steaming chamber 233 into which-steam is introduced into the bottom portion thereof through line 234. This steaming operation acts to remove oil from the catalyst particles before they are passed tothe regeneration zone. During this steaming operation, some catalyst particles are carried along with the steam and the outgoing steam plus the fine catalyst particles are passed through line 236 and introduced into the bottom portion of a seclond separating device 238. The reaction product vapors leaving the first separator 2|6 and passing through line 2 I 8 are also introduced into the lower portion of the second separating device 238.

The second separating device 238 is provided with a plurality of inclined baffles 246 and cones 24B for providing Contact between the reflux liquid and the gases and vapors. Reflux liquid is introduced into the upper portion of the separating device 238 by means of line 252. The scrubbed gases and vapors containing gasoline constituents leave the top of the second separating device 238 by'means of line 252 and are further treated as desired to remove desired products therefrom.

The reflux oil and a condensed heavy fraction containing catalyst particles arewithdrawn from the bottom of the separating device 238 and passed through line 256 and cooler 250 and then to a continuous filter or the like 282. The filtered oil is passed through line 263 and cooler 264 and then returnedto the top of the separating device 238 as reilux liquid. The iiltered catalyst particles are removed from the lter through line 2661and may be further treated in any suitable manner before they are passed to the regeneration zone. Or, they may be returned to the reaction zone 206. A portion of the filtered oil may be withdrawn through line 263. If desired, fresh reflux liquid gri'azy be introduced into line 252 by means of line The steamed catalyst particles leaving the steaming chamber 233 are withdrawn from the bottom of the chamber through line 276 and passed through line 218 to a suitable regeneration zone such as shown in Figures l and 2 of the drawings. If desired, all or part of the steamed catalyst particles passing through line 216 may be passed through line 280 and mixed with the slurry of reiiuX liquid and catalyst particles passing through line 256 and then filtered in the filter 262 and further treated as above described.

While I have shown certain arrangements of apparatus in the drawings. it is to be understood that these are by way of example only and that various modifications and changes may be made without departing from the spirit of my invention. One example of converting oil will now be given: In Figure l a relatively heavy hydrocarbon oil such as gas oil'is vapor-ized by passing through the heater I4. The hydrocarbon vapors are preferably at a temperature of about 850 F. to 1000 F. and under a pressure between about atmospheric and 300 lbs/sq. in. but preferably about` 60 lbs/sq. in. The catalyst used is preferably an activated clay such as an acid treated bentonite. The mixture of powdered clay catalyst and hydrocarbon vapors remain in the reaction chamber for about 2 seconds to 2 minutes. The ratio of catalyst oil may Vary from about .5 volume to 20 volumes of catalyst per volumev oi oil.

In the regeneration step, the temperature of regeneration is maintained below about 1200 F. and the pressure may range from about atmospheric to about 300 lbs/sq. in. The time of regeneration may vary from about 10 seconds to 20 minutes.

The above example is given by way of illustration only and I am not to be limited to this example as other temperatures and pressuresvmay be used for different oil stocks and for different catalysts, Other cracking catalysts such as active, natural or synthetic clays, gels containing silica and alumina or the like may be used.

The reaction products leaving the Vtop of the second separating device 'i8 in Figure 1 may range from about 600 F. to 875 F. The reflux liquid y is preferably at a temperatureof about 400l F. The amount of heavy fractions condensed fromr the reaction product vapors under these conditions is about 2%. About the same conditions are maintained in separator |68 in Figure 2 and separator 238 in' Figure 3.

While I have described a preferred form of my invention and modications thereof, it is to be understood that these are by way of illustration only and Various changes may be made within the scope of the invention without departing from the spirit of my invention.

I claim:

1. A method of treating hydrocarbons which comprises passing hydrocarbon vapors through a horizontally arranged reaction zone together with powdered catalyst, maintaining the reaction zone at an elevated temperature to effect the desired extent of conversion of the hydrocarbons, the powdered catalyst .in part settling on the bottom of the reaction zone, removing products of conversion containing powdered catalyst from said reaction zone, separating a large part of the powdered `catalyst from the vapors in a first separation step, passing the vapors to a second separation step, scrubbing catalyst from the vapors in the second separation step with a hot scrubbing oil and removing the separated catalyst from the scrubbing oil.

2. A method according to claim 1, wherein at least a portion of the catalyst separated in the 'first separation step is returned to said reaction zone.`

3. A method of treating hydrocarbons which comprises passing hydrocarbon vapors and powdered catalyst through a reaction zone maintained-at an elevated temperature to effect the desired extent of conversion, separating reaction product vapors from a large portion of the powdered catalyst in a first separating Zone, returning atleast a portion of the separated powdered catalyst without regeneration to the reaction zone at a plurality of spaced points for increasing the ratiov of catalyst to hydrocarbon vapors passing through said reaction zone, passing the reaction product vapors at substantially undiminished temperature to a scrubbing zone, scrubbing the separated reaction product vapors with a hot scrubbing oil to remove residual powdered catalyst from the reaction product vapors and separating the catalyst particles from the scrubbing oil.

JACKSON R. SCI-IONBERG. 

